WO2016062206A1 - Procédé de dépôt électrochimique horizontal de métal - Google Patents

Procédé de dépôt électrochimique horizontal de métal Download PDF

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WO2016062206A1
WO2016062206A1 PCT/CN2015/091697 CN2015091697W WO2016062206A1 WO 2016062206 A1 WO2016062206 A1 WO 2016062206A1 CN 2015091697 W CN2015091697 W CN 2015091697W WO 2016062206 A1 WO2016062206 A1 WO 2016062206A1
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Prior art keywords
metal
sheet substrate
electrochemical deposition
electrolyte solution
anode
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PCT/CN2015/091697
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English (en)
Chinese (zh)
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季静佳
覃榆森
朱凡
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苏州易益新能源科技有限公司
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Priority to EP15852603.8A priority Critical patent/EP3206236B1/fr
Priority to JP2017521075A priority patent/JP6431980B2/ja
Priority to US15/519,782 priority patent/US20170250295A1/en
Publication of WO2016062206A1 publication Critical patent/WO2016062206A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/011—Electroplating using electromagnetic wave irradiation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/001—Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/026—Electroplating of selected surface areas using locally applied jets of electrolyte
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/028—Electroplating of selected surface areas one side electroplating, e.g. substrate conveyed in a bath with inhibited background plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/005—Contacting devices

Definitions

  • the present invention relates to a method of electrochemically depositing a metal, and more particularly to a method of performing a gap or continuous horizontal electrochemical deposition of a metal on a sheet substrate.
  • the method of electrochemically depositing metal of the present invention has a wide range of applications and is suitable for mass production.
  • the most widely used method for forming metal electrodes of crystalline silicon solar cells is to use a screen printing technique to print metal pastes such as silver paste and aluminum paste on the negative and positive surfaces of crystalline silicon solar cells, respectively. These metal pastes are sintered at a high temperature to form metal electrodes of crystalline silicon solar cells.
  • the method has the advantages of simple process and convenient mass production.
  • Metallic copper is one of the ways to replace expensive silver paste. However, at high temperatures, metal copper diffused into crystalline silicon significantly reduces the minority carrier lifetime of crystalline silicon. Therefore, metallic copper can only be deposited on a crystalline silicon solar cell at a low temperature, thereby generating an electrode of a crystalline silicon solar cell.
  • one method of replacing the silver paste with metallic copper is to first screen a small amount of silver paste on the negative electrode of the crystalline silicon solar cell, and after sintering at a high temperature, the silver paste and the crystalline silicon solar cell are used.
  • the negative electrode forms an ohmic contact, that is, a metal electrode of a crystalline silicon solar cell is generated, and then metal copper is electrochemically deposited on the silver paste to meet the requirements for collecting and transmitting the electric energy generated by the crystalline silicon solar cell.
  • Another method of replacing silver paste with metallic copper is to electrochemically deposit various metals, such as nickel-copper-silver stacks, on a crystalline silicon solar cell, ultimately resulting in a metal electrode of a crystalline silicon solar cell.
  • various metals such as nickel-copper-silver stacks
  • electrochemical deposition of metal is a simple method and low production cost to produce a metal electrode of a crystalline silicon solar cell. Therefore, the use of electrochemical methods to deposit metal on crystalline silicon solar cells is currently a very active field of technology research and development.
  • Patent CN101257059A discloses a method of electrochemically depositing a metal on a negative electrode surface of a crystalline silicon solar cell by using a potential difference generated by a crystalline silicon solar cell after being irradiated, that is, a method of photoinduced electrochemical deposition of a metal. Since this method lacks the positive electrode electronic contact technology of a reliable crystalline silicon solar cell, the method can only be obtained in the laboratory. use.
  • Patent CN102083717A discloses a positive electrode electronic contact method in a crystalline silicon solar cell, which enables the application of electrochemically deposited metal in the mass production of crystalline silicon solar cells.
  • this method has two drawbacks.
  • the negative electrode surface of the crystalline silicon solar cell under the action of the upper metal spring roller, continuously rubs against the lower roller, not only damages the negative electrode surface of the crystalline silicon solar cell, but also deposits metal deposited by electrochemical deposition of metal. The electrodes also cause some damage.
  • Another disadvantage is that the method has limitations in its application, which is limited to applications on crystalline silicon solar cells with screen printed aluminum backfields.
  • the back passivation technology of crystalline silicon solar cells will gradually replace the aluminum back field technology of the conventional crystalline silicon solar cells.
  • the anode of the crystalline silicon solar cell can also be used to form an electrode of a crystalline silicon solar cell using an electrochemical deposition method.
  • the two methods of electrochemically depositing metals disclosed above can only be performed by electrochemically depositing metal on the negative electrode of a crystalline silicon solar cell.
  • both the negative electrode of the crystalline silicon solar cell and the electrode of the positive electrode need to be electrochemically deposited to form an electrode, it is necessary to separately perform electrochemical deposition of the metal on the negative electrode and the positive electrode, which is disadvantageous for mass production.
  • the present invention provides a method of performing horizontal electrochemical deposition of a metal on a sheet substrate.
  • One of the objects of the present invention is to find a method for forming a metal electrode on a crystalline silicon solar cell by electrochemically depositing a metal, in which the negative electrode surface of the crystalline silicon solar cell does not contact any solid during the electrochemical deposition of the metal.
  • the negative electrode surface of the crystalline silicon solar cell and the metal are protected from damage due to friction between the solids after being deposited.
  • Another object of the present invention is to find a method for forming a metal electrode on a crystalline silicon solar cell by electrochemically depositing a metal, which can simultaneously perform electrochemical deposition of a metal on a negative electrode surface and a positive electrode surface of a crystalline silicon solar cell. Simplify the metal electrode formation process of a double-sided crystalline silicon solar cell.
  • a further object of the present invention is to find a method for producing a metal electrode on a crystalline silicon solar cell using an electrochemically deposited metal, which has wide applicability and utility, that is, the method can be used alone in the p-type of a solar cell. Electroplating on the electrodes can also be performed by electroplating on the n-type electrode of the solar cell alone or on both the p-type electrode and the n-type electrode of the solar cell.
  • a final object of the present invention is to further seek a method for electrochemically depositing metal on other thin substrates, in addition to a method for forming a metal electrode on a crystalline silicon solar cell using an electrochemically deposited metal, and further expanding the method for electrochemically depositing metal on other thin substrates.
  • the scope of application of the present invention is to further seek a method for electrochemically depositing metal on other thin substrates, in addition to a method for forming a metal electrode on a crystalline silicon solar cell using an electrochemically deposited metal, and further expanding the method for electrochemically depositing metal on other thin substrates.
  • the present invention discloses a method of performing electrochemical deposition of a metal on a sheet substrate.
  • the method for performing electrochemical deposition of metal on a sheet substrate disclosed by the present invention is to place an upper metal anode in an electrochemical deposition metal process on top of an electrolyte solution on a surface of a sheet substrate to be electrochemically deposited, or elsewhere
  • the electrolyte solution flows to the upper surface of the sheet substrate after passing through the upper metal anode.
  • the upper metal anode undergoes an oxidation reaction under the action of a positive potential, and the electrons are generated to form metal ions, and then flow down to the upper surface of the sheet substrate with the electrolyte solution.
  • the metal ions in the electrolyte solution acquire electrons on the surface of the cathode on the sheet substrate to form a solid metal and deposit on the cathode surface of the sheet substrate.
  • One of the advantages of the present invention is that the metal ions generated by the oxidation reaction on the upper metal anode are transported to the surface of the cathode in time by the flowing electrolyte solution, thereby improving the effectiveness of the redox reaction in the electrochemical deposition of the metal. Sex. Also, in the electrochemical deposition metal method of the present invention, the surface of the cathode is continuously washed by the top-down electrolyte solution, so that the concentration of the metal ions is always uniform at any point on the surface of the cathode, thereby improving the deposition of the metal. Uniformity. Further, the process of the cathode surface being continuously washed by the top-down electrolyte solution can also prevent any gas that may be generated from accumulating on the surface of the cathode.
  • Another advantage of the present invention is that the upper surface of the sheet substrate may not be in contact with any solid during the electrochemical deposition of the metal of the present invention.
  • This advantage of the present invention is more pronounced when the electrochemical deposition metal method of the present invention is applied to the deposition of a metal on the surface of a crystalline silicon solar cell anode (n-type surface), i.e., the sheet substrate is a crystalline silicon solar cell.
  • the main light receiving surface of most crystalline silicon solar cells is a negative electrode, and the quality of the negative receiving surface of the negative electrode is directly related to the photoelectric conversion efficiency of the crystalline silicon solar cell. Since the electrochemical deposition metal method of the present invention makes the negative electrode surface of the crystalline silicon solar cell not in contact with any solid, the possibility that the negative electrode surface of the crystalline silicon solar cell is damaged is effectively avoided.
  • a crystalline silicon solar cell generates electrical energy under illumination.
  • a method of photoinduced electrochemical deposition of a metal can be employed.
  • the electrochemical deposition metal method of the present invention has a small liquid thickness of the electrolyte solution above the negative electrode of the crystalline silicon solar cell, which reduces the absorption of light by the electrolyte solution.
  • the illumination energy can be utilized to the utmost.
  • the electrochemical deposition metal method of the present invention can be used very flexibly in practical applications.
  • the electrochemical deposition metal method of the present invention can be carried out using a conventional external power source method.
  • the electrochemical deposition metal method of the present invention can also be carried out using a method of photoinduced electrochemical deposition of a metal.
  • conventional external power source methods and photoinduced electrochemical deposition metal methods can be used together to implement the electrochemical deposition metal method of the present invention.
  • the position of the metal anode can be more selected under the condition that the circuit in the electrochemical deposition metal process is closed.
  • the metal anode can be made not to directly face the negative electrode surface of the electrochemically deposited metal.
  • the electrochemical deposition metal method of the present invention can perform the electrochemical deposition metal method of the present invention on the negative electrode surface of the crystalline silicon solar cell, or on the positive electrode of the crystalline silicon solar cell.
  • the electrochemical deposition metal method of the present invention can be carried out simultaneously on the negative electrode and the positive electrode of a crystalline silicon solar cell. Therefore, one of the important advantages of the present invention is that the method of electrochemically depositing metal of the present invention makes it possible to simultaneously perform electrochemical deposition of metal on the positive and negative electrodes of a solar cell.
  • the electrochemical deposition metal method of the present invention is well suited for use in equipment having a horizontally advanced structure.
  • the horizontal advancement device makes the loading and unloading steps very simple and is more conducive to the automation of the entire production line.
  • Another advantage of the present invention is that the apparatus for carrying out the electrochemical deposition metal process of the present invention is very simple.
  • an electrolyte solution is disposed on the sheet substrate, and the self-weight of the electrolyte solution layer enables the sheet substrate to be closely attached to the conductive roller supporting the same, thereby implementing the present invention.
  • the electrode solution of the electrochemical deposition metal method does not need to have an upper roller, which not only simplifies the structure of the device, but also saves the cost of the device.
  • the electrochemical deposition metal method of the present invention is suitable for continuous electrochemical deposition of metals, as well as for gap electrochemical deposition of metals. That is to say, with the electrochemical deposition metal method of the present invention, the results can be communicated regardless of whether the metal is continuously deposited by electrochemical deposition or the metal is deposited by gap electrochemical deposition. For example, the results of the gap electrochemical deposition metal method of the present invention in the laboratory can be applied to mass-produced horizontally advanced equipment without any modification.
  • Figure 1 Schematic cross-sectional view of one of the applications of the electrochemical deposition metal method of the present invention on a p-type screen printing battery
  • Figure 2 Schematic cross-sectional view of one of the applications of the electrochemical deposition metal method of the present invention on a conductive sheet substrate
  • Figure 3 Schematic cross-sectional view of one of the applications of the electrochemical deposition metal method of the present invention on an n-type double-sided battery
  • FIG. 4 Schematic cross-section of one of the applications of the electrochemical deposition metal method of the present invention on a p-type solar cell
  • Figure 5 Schematic cross-sectional view of one of the applications of the electrochemical deposition metal method of the present invention on a sheet substrate.
  • Figure 1 illustrates one embodiment of a method of performing the electrochemical deposition of metals of the present invention using a photoinduced electrochemical deposition metal process.
  • the sheet substrate 90 is a p-type crystalline silicon screen printed solar cell.
  • the so-called p-type crystalline silicon screen printing solar cell means that the metal electrode 320 of the positive electrode of the battery is formed by screen printing aluminum paste and then sintering.
  • the screen printed aluminum paste substantially covers the majority of the positive electrode area of the solar cell.
  • the negative electrode surface 310 of the p-type crystalline silicon screen printing solar cell 90 receives light from the light source 80, electrical energy is generated, and a positive potential generated on the metal electrode 320 is transmitted to the electrochemically deposited metal of the present invention through the conductive roller 60 supporting it.
  • the upper metal anode 20 of the electrochemical deposition metal method of the present invention undergoes an oxidation reaction to lose electron-generated metal ions under the action of a positive potential of a p-type crystalline silicon screen-printed solar cell.
  • the generated metal ions flow down with the electrolyte solution 40 to the negative electrode surface 310 of the p-type crystalline silicon screen printing solar cell 90, and the metal ions in the electrolyte solution 40 are p-type crystalline silicon screen printing solar cells under the upper metal anode 20.
  • the negative electrode surface 310 of 90 is free of electrons on the insulated area, and a reduction reaction is generated to form a metal and deposited on the uninsulated area of the negative electrode surface 310 of the p-type crystalline silicon screen printing solar cell, thereby completing one in the system.
  • a photoinduced electrochemical redox reaction of the complete electrochemical deposition metal process of the present invention is
  • the method of electrochemically depositing metal of the present invention may also be externally added to the embodiment of FIG. power supply.
  • the positive electrode of the external power source is coupled to the upper metal anode 20
  • the negative electrode of the external power source is coupled to the conductive roller 60
  • the potential of the external power source is used to increase the power. The potential difference of a chemically deposited metal.
  • the method of electrochemically depositing metal of the present invention is to place the upper metal anode 20 above the liquid level 42 of the electrolyte solution 40.
  • the upper metal anode 20 can be formed in a tubular form.
  • the electrolyte solution 40 may contact the inner surface of the upper metal anode 20, directly flowing from the inside of the upper metal anode 20 to the negative electrode of the sheet substrate 90 of the electrochemical deposition metal method of the present invention.
  • Surface 310 By forming the upper metal anode 20 in the electrochemical deposition metal method of the present invention into a tubular form, the apparatus for carrying out the electrochemical deposition metal method of the present invention can be simplified.
  • the upper metal anode 20 can be placed within the electrolyte solution conduit 30, and the electrolyte solution conduit 30 can be a tube of inert material, such as a plastic tube, or a glass tube or the like.
  • the electrolyte solution 40 contacts the outer surface of the metal anode 20, and flows from the electrolyte solution conduit 30 to the negative electrode upper surface 310 of the sheet substrate 90 of the solar cell of the electrochemical deposition metal method of the present invention.
  • This structural design of the electrochemical deposition metal method of the present invention can improve the utilization of the upper metal anode 20 of the electrochemical deposition metal method of the present invention.
  • the upper metal anode 20 can be higher than the liquid level 42 of the electrolyte solution 40. In other embodiments, the upper metal anode 20 above the liquid level 42 of the electrolyte solution 40 may also be as low as the liquid level 42 of the electrolyte solution 40.
  • the electrolyte solution 40 flowing out of the negative electrode upper surface 310 of the sheet substrate 90 is collected by the electrolyte solution tank 50 and returned to the electrolyte solution catheter 30 to complete the electrochemical reaction metal flowing through the upper metal anode 20 of the present invention.
  • the electrolyte solution of the upper surface 310 of the negative electrode of the sheet substrate 90 of the deposition metal method is circulated.
  • the conductive roller 60 supports the sheet substrate 90.
  • the conductive roller 60 can be rotated left and right to make the metal deposited by the electrochemical deposition metal method of the present invention more uniform.
  • the conductive roller 60 can be rotated in one direction. For example, in some mass production equipment having a horizontally advanced structure, the conductive roller 60 rotating in one direction can be continuously completed. The method of electrochemically depositing a metal of the present invention.
  • the conductive roller 60 may be made of a metal material. In some embodiments of the present invention, a majority of the electrically conductive area of the metal conductive roller may be covered with an insulating material to reduce the loss of potential difference due to a short circuit during the implementation of the electrochemical deposition metal method of the present invention. . In other embodiments of the invention, the conductive roller 60 may also be of an insulating material. In these embodiments, a conductive material may be used to couple the area of the portion of the conductive roller 60 that needs to be electrically conductive to achieve the effect of the conductive roller.
  • the conductive roller 60 can be modified to a fixed number of fixed conductive support points, particularly when the gap electrochemical deposition metal method is employed in the electrochemical deposition metal method of the present invention.
  • the use of a certain amount of solid conductive support enables the implementation of the electrochemical deposition metal method of the present invention to be simpler.
  • the method of horizontal electrochemical deposition of metals of the present invention can be extended to other sheet substrates.
  • the sheet substrate 10 is a conductor, i.e., the conductive property between the upper surface and the lower surface of the sheet substrate 10 is the conductive property of the sheet substrate 10 itself. Determined.
  • the upper metal anode of the present invention is not an upper metal anode in a general physical sense, but an upper metal anode in the electrochemical deposition metal relative to the cathode of the upper surface of the sheet substrate 10.
  • the metal anode which flows to the upper surface of the sheet substrate 10 after the electrolyte solution contacts the metal anode is referred to as an upper metal anode.
  • the upper metal anode can be placed in any suitable location. In the embodiment of Figure 2, the upper metal anode 20 is placed in the electrolysis The bottom of the solution tank 50.
  • the electrolyte solution 40 is transferred to the upper surface of the sheet substrate 10 through the infusion tube 32 after contacting the metal anode 20.
  • the infusion tube 32 can be mounted above the electrolyte solution level 42 or it can be mounted very close to the electrolyte solution level 42 and can even be as low as the electrolyte solution level 42.
  • the upper metal anode 20 of the electrochemical deposition metal method of the present invention is coupled to the anode of the power source 70, and the conductive roller 60 is coupled to the cathode of the power source 70.
  • the upper metal anode 20 undergoes an oxidation reaction to lose electron-generated metal ions.
  • the generated metal ions flow down to the upper surface 300 of the sheet substrate 10 with the electrolyte solution 40, and metal ions in the electrolyte solution 40 get electrons on the upper surface of the sheet substrate 10, and a reduction reaction occurs to form a metal and deposit on the cathode surface of the sheet substrate 10.
  • the sheet substrate 10 is continuously supplied with electrons from the negative electrode of the power source 70 through the conductive roller 60, thereby completing an electrochemical electrochemical redox reaction of the complete electrochemical deposition metal method of the present invention in the system.
  • the sheet substrate 10 material may not be a conductor, such as a printed wiring board.
  • the sheet substrate 10 may cause the sheet substrate 10 to generate a cathode surface by a specific process such as a method using conductive holes, under the action of the conduction of the conductive roller 60 and the negative potential of the negative electrode of the power source 70.
  • Inventive method of electrochemically depositing metals are described in detail below.
  • the sheet substrate 10 is a rigid substrate, such as a rigid printed wiring board.
  • the sheet substrate 10 can also be a flexible substrate, such as a flexible printed wiring board. Since the electrochemical deposition metal method of the present invention does not have solids in contact with the upper surface of the sheet substrate 10 and does not cause any damage to the upper surface of the sheet substrate, the electrochemical deposition metal method of the present invention is particularly suitable for electrochemically performing a flexible substrate. Deposit metal.
  • the electrochemical deposition metal method of the present invention can simultaneously perform electrochemical deposition of metal on the two surfaces of the sheet substrate by using the potential difference generated by the external power source and the light-inducing power source.
  • 3 is a view showing an embodiment of the method of electrochemically depositing metal of the present invention, in which an electroless deposition metal is simultaneously performed on a positive electrode and a negative electrode of an n-type crystalline silicon solar double-sided battery having a positive light-receiving surface as a positive electrode.
  • the sheet substrate is an n-type crystalline silicon solar double-sided battery 200 having a main light receiving surface as a positive electrode.
  • the light source 80 can be moved below the crystalline silicon solar cell 200.
  • the light generated by the light source 80 passes through the through-tube electrolyte solution container 50, and is irradiated onto the main light-receiving surface of the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is the positive electrode.
  • the upper metal anode 20 and the lower metal anode 24 are simultaneously above the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is a positive electrode.
  • the electrolyte solution 40 is transferred through the infusion tube 34 to the upper surface of the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is the positive electrode, that is, its negative surface 350, after contacting the upper metal anode 20.
  • the electrolyte solution 40 is transferred through the infusion tube 36 to the n-type crystal whose main light receiving surface is the positive electrode.
  • the lower surface of the silicon solar double-sided battery 200 that is, its positive surface 360.
  • the infusion tube 34 can be mounted above the electrolyte solution level 42 or it can be mounted very close to the electrolyte solution level 42 and can even be as low as the electrolyte solution level 42.
  • the infusion tube 36 is mounted below the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is a positive electrode.
  • the optimized mounting method is to install the infusion tube 36 on the lower surface of the n-type crystalline silicon solar double-sided battery 200 which is very close to the main light receiving surface.
  • the apparatus for carrying out the method of electrochemically depositing metal of the present invention in mass production is simplified.
  • the positive electrode of the external power source 70 is connected to the lower metal anode 24, and the negative electrode of the external power source 70 is connected to the conductive roller 60 of the support sheet substrate 200.
  • the positive electrode 360 of the n-type crystalline silicon solar double-sided battery 200 whose main receiving surface is positive is conducted under the action of the external power source 70 and the conductive roller 60 supporting the sheet substrate 200, and in the electrochemical reaction, relative to the lower metal anode 24 a cathode.
  • the metal ions in the electrolyte solution 40 receive electrons on the uninsulated area of the positive electrode 360 of the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is the positive electrode, and then form an n-type metal deposited on the main light receiving surface as a positive electrode.
  • the positive electrode 360 of the crystalline silicon solar double-sided battery 200 is not insulated on the area.
  • the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is a positive electrode generates electric energy.
  • the electrolyte solution 40 flows down through the upper metal anode 20 to the surface of the negative electrode 350 of the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is the positive electrode, the metal ions in the electrolyte solution 40 receive electrons. After the metal is formed, it is deposited on the negative electrode 350 of the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is the positive electrode, without being insulated.
  • the upper metal anode 20 is formed by the positive electrode 360 of the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is a positive electrode, and the metal anode is generated by the oxidation of the conductive roller 60 supporting the thin substrate 200. And dissolved in the electrolyte solution 40 to complete a complete electrochemical redox reaction.
  • the system simultaneously performs light-induced electrochemical deposition of metal on the surface of the anode 350 on the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is positive.
  • the metal is electrochemically deposited on an external power source on the surface of the positive electrode 350.
  • the potential difference determines the rate of the electrochemical reaction.
  • the generated potential of the solar cell 200 can be adjusted by adjusting the light intensity of the light source 80, thereby controlling the negative electrode 350 of the solar cell 200.
  • the rate at which metal is deposited it is also possible to control the rate at which metal is deposited on the positive electrode 360 of the solar cell 200 by adjusting the potential of the power source 70, and finally to attain the rate of electrochemically depositing metal at the positive electrode 360 and the negative electrode 350 of the solar cell 200.
  • the upper metal anode 20 may be electrically conductive from the positive electrode 360 of the n-type crystalline silicon solar double-sided battery 200 coupled to the main light-receiving surface as a positive electrode, that is, the support sheet substrate 200.
  • the roller 60 is instead coupled to the lower metal anode 24.
  • This connection method can reduce the dependence of the rate of electrochemical deposition of the metal of the negative electrode 350 of the n-type crystalline silicon solar double-sided battery 200 whose main light receiving surface is positive on the light intensity of the light source 80.
  • the electrochemical deposition metal method of the present invention can simultaneously perform electrochemical deposition of metal on the two surfaces of the p-type crystalline silicon solar cell by utilizing the potential difference generated by the external power source and the light-inducing power source.
  • 4 shows an embodiment of the method of electrochemically depositing metal of the present invention, in which an electroless deposition of a metal is simultaneously performed on a positive electrode and a negative electrode of a p-type crystalline silicon solar cell whose main light receiving surface is a negative electrode.
  • the sheet substrate is a p-type crystalline silicon solar cell 200 having a main light receiving surface as a negative electrode.
  • the p-type crystalline silicon solar cell 200 in which the main light receiving surface is a negative electrode is supported by the insulating roller 60. Since the main light receiving surface of the battery is a negative electrode, in carrying out the method of electrochemically depositing metal of the present invention, as shown in FIG. 4, the light source 80 can be moved below the crystalline silicon solar cell 200. The light generated by the light source 80 is transmitted through the transparent electrolyte solution container 50, and is irradiated onto the main light receiving surface of the p-type crystalline silicon solar cell 200 whose main light receiving surface is the negative electrode.
  • the upper metal anode 24 and the lower metal anode 20 are respectively placed above and below the p-type crystalline silicon solar cell 200 whose main light receiving surface is a negative electrode.
  • the upper metal anode 24 is placed on the upper surface of the p-type crystalline silicon solar cell 200 whose main light receiving surface is the negative electrode, but does not contact the upper surface of the p-type crystalline silicon solar cell 200 whose main light receiving surface is the negative electrode. .
  • the electrolyte solution 40 flows to the upper surface of the p-type crystalline silicon solar cell 200 whose main light receiving surface is the negative electrode, that is, its positive surface 360.
  • the upper metal anode 24 is not in physical contact with the upper surface of the p-type crystalline silicon solar cell 200 whose main light receiving surface is a negative electrode, the upper surface of the p-type crystalline silicon solar cell 200 having the upper metal anode 24 and the main light receiving surface as a negative electrode The distance is small, and when the electrolyte solution is present on the upper surface of the p-type crystalline silicon solar cell 200 whose main receiving surface is the negative electrode, the upper metal anode 24 is in contact with the surface of the electrolyte solution.
  • the lower metal anode 20 is placed under the lower surface of the p-type crystalline silicon solar cell 200 whose main light receiving surface is a negative electrode, and is directly immersed in the electrolytic solution 40.
  • the external electrode is externally disposed.
  • the positive electrode of the power source 70 is connected to the upper metal anode 24, and the negative electrode conductive roller 66 of the external power source 70 is connected.
  • the positive electrode 360 of the p-type crystalline silicon solar cell 200 whose main receiving surface is the negative electrode is conducted under the action of the external power source 70 and the conductive roller 66. In the electrochemical reaction, it is a cathode with respect to the upper metal anode 24.
  • the metal ions in the electrolyte solution 40 receive electrons on the uninsulated area on the positive electrode 360 of the p-type crystalline silicon solar cell 200 whose main light-receiving surface is the negative electrode, and then generate p-type crystalline silicon whose metal is deposited on the main light-receiving surface as a negative electrode.
  • the positive electrode 360 of the solar cell 200 is not on the insulated area.
  • the p-type crystalline silicon solar cell 200 whose main light receiving surface is the negative electrode generates electric energy.
  • the metal ions in the electrolyte solution 40 receive electrons on the surface of the negative electrode 350 of the p-type crystalline silicon solar cell 200 whose main light-receiving surface is a negative electrode, and are deposited on the negative electrode of the p-type crystalline silicon solar cell 200 whose main light-receiving surface is a negative electrode.
  • the 350 is not insulated on the area.
  • the lower metal anode 20 is formed by the conduction of the conductive roller 66 by the conduction of the conductive roller 66 under the action of the positive electrode 360 of the p-type crystalline silicon solar cell 200 whose main light receiving surface is the negative electrode, and then generates metal ions and dissolves in the electrolyte solution 40. , complete a complete electrochemical redox reaction.
  • the system simultaneously performs light-induced electrochemical deposition of the metal on the surface of the anode 350 and the anode for the p-type crystalline silicon solar cell 200 whose main light-receiving surface is the negative electrode.
  • An external power source on the 360 surface electrochemically deposits metal.
  • the potential difference determines the rate of the electrochemical reaction.
  • the generated potential of the solar cell 200 can be adjusted by adjusting the light intensity of the light source 80, thereby controlling the negative electrode 350 of the solar cell 200.
  • the rate at which metal is deposited it is also possible to control the rate at which metal is deposited on the positive electrode 360 of the solar cell 200 by adjusting the potential of the power source 70, and finally to attain the rate of electrochemically depositing metal at the positive electrode 360 and the negative electrode 350 of the solar cell 200.
  • the method of horizontal electrochemical deposition of metals of the present invention can be extended to simultaneously perform electrochemical deposition of metals on both surfaces of any sheet substrate.
  • the sheet substrate 100 is an insulator, and the conductive property between the upper surface and the lower surface of the sheet substrate 100 is realized by the conductive holes 400 that couple the upper and lower surfaces.
  • the method of electrochemically depositing metal of the present invention is to place the upper metal anode 20 above the liquid level 42 of the electrolyte solution 40.
  • the upper metal anode 20 can be formed into a tubular form.
  • the electrolyte solution 40 may flow through the inner surface of the metal anode 20 directly from the inside of the metal anode 20 to the upper surface of the sheet substrate 100 of the electrochemical deposition metal method of the present invention. .
  • the metal anode 20 can be placed within the electrolyte solution conduit 30, and the electrolyte solution conduit 30 can be a tube of inert material, such as a plastic tube, or a glass tube or the like.
  • the electrolyte solution 40 flows through the outer surface of the metal anode 20, and flows from the inside of the electrolyte solution conduit 30 to the upper surface of the sheet substrate 100 of the electrochemical deposition metal method of the present invention.
  • This structural design of the electrochemical deposition metal method of the present invention can improve the utilization of the metal anode 20 of the electrochemical deposition metal method of the present invention.
  • the metal anode 20 can be higher than the liquid level 42 of the electrolyte solution 40. In other embodiments, the metal anode 20 above the liquid level 42 of the electrolyte solution 40 may also be as low as the liquid level 42 of the electrolyte solution 40. In this embodiment, the lower metal anode 22 is placed at the bottom of the vessel 50 of the electrolyte solution. The liquid surface of the electrolyte solution 40 in the electrolyte solution container 50 just contacts the lower surface of the sheet substrate 100.
  • the upper metal anode 20 and the lower metal anode 22 of the electrochemical deposition metal method of the present invention are simultaneously coupled to the positive electrode of the power source 70, and the conductive roller 60 supporting the sheet substrate 100 is coupled to the negative electrode of the power source 70.
  • the upper metal anode 20 and the lower metal anode 22 are subjected to an oxidation reaction under the action of a positive potential of the power source 70 to lose electron-generated metal ions.
  • the generated metal ions flow down to the upper surface of the sheet substrate 100 with the electrolyte solution 40, or migrate from the bottom to the lower surface of the sheet substrate by the electrolyte 40 under the action of the potential difference, and the metal ions in the electrolyte solution 40 are on the sheet substrate 100.
  • the cathode surface is electron-derived, and a reduction reaction occurs to form a metal and is deposited on the cathode surface of the sheet substrate 100.
  • the sheet substrate 100 continuously obtains electrons from the negative electrode of the power source 70 by supporting the conductive roller 60 of the sheet substrate 100, thereby completing an electrochemical electrochemical redox reaction of the entire electrochemical deposition metal method of the present invention in the system.
  • the electrochemical deposition metal method of the present invention may also adopt two external power sources to respectively perform electrochemical deposition of metal on the upper and lower surfaces of the sheet substrate, and respectively control the electrochemical deposition metal of the upper and lower surfaces of the sheet substrate. s speed.
  • the upper metal anode 20 is coupled to the anode of one of the external power sources
  • the lower metal anode 22 is coupled to the anode of the other external power source
  • the cathodes of the two external power sources are simultaneously coupled to the conductive roller 60 of the support sheet substrate 100.
  • the upper metal anode 20 and the lower metal anode 22 respectively undergo an oxidation reaction to lose electron-generated metal ions under the action of the positive potentials of the two power sources.
  • the generated metal ions flow down to the upper surface of the sheet substrate 100 with the electrolyte solution 40, or migrate from the bottom to the lower surface of the sheet substrate by the electrolyte 40 under the action of the potential difference, and the metal ions in the electrolyte solution 40 are on the sheet substrate 100.
  • the cathode surface is electron-derived, and a reduction reaction occurs to form a metal and is deposited on the cathode surface of the sheet substrate 100.
  • the sheet substrate 100 is continuously obtained from the negative electrodes of the two external power sources by the conductive rollers 60 supporting the sheet substrate 100, thereby completing a complete electrochemical redox reaction of the electrochemical deposition metal method of the present invention in the system.
  • the method of electrochemically depositing metal of the present invention can achieve the rate of electrochemically depositing metals independently on the upper and lower surfaces of the sheet substrate 100, respectively.
  • the upper metal anode 20 and the lower metal anode 22 of the method of electrochemically depositing metals of the present invention may also use an insoluble anode.
  • the metal ions in the electrochemically deposited metal of the present invention are not produced by the upper metal anode 20 and the lower metal anode 22, but by the metal oxide dissolved in the electrolyte solution 40.

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Abstract

L'invention porte sur un procédé de dépôt électrochimique de métal sur un substrat en feuille (90), une anode métallique supérieure (20) étant placée au-dessus du niveau de liquide (42) d'une solution électrolytique (40) et lorsque la solution électrolytique (40) entre en contact avec l'anode métallique supérieure (20), cette dernière s'écoule de haut en bas jusqu'à la surface supérieure du substrat en feuille (90). L'anode métallique supérieure (20) est soumise à une réaction d'oxydation sous l'effet d'un potentiel positif, perdant des électrons pour former des ions métalliques qui s'écoulent ensuite vers le bas avec la solution électrolytique (40) jusqu'à la surface supérieure (310) du substrat en feuille (90). Les ions métalliques présents dans la solution électrolytique (40) obtiennent des électrons au niveau de la cathode sur le substrat en feuille (90), et un métal est produit et déposé sur la surface de cathode (310) du substrat en feuille (90).
PCT/CN2015/091697 2014-10-20 2015-10-11 Procédé de dépôt électrochimique horizontal de métal WO2016062206A1 (fr)

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EP15852603.8A EP3206236B1 (fr) 2014-10-20 2015-10-11 Procédé de dépôt électrochimique horizontal de métal
JP2017521075A JP6431980B2 (ja) 2014-10-20 2015-10-11 金属の水平電気化学堆積法
US15/519,782 US20170250295A1 (en) 2014-10-20 2015-10-11 Method for horizontally electrochemically depositing metal

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CN201410557444.5A CN105590987B (zh) 2014-10-20 2014-10-20 一种水平电化学沉积金属的方法
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CN105590987B (zh) 2022-06-14
CN105590987A (zh) 2016-05-18
EP3206236A1 (fr) 2017-08-16
US20170250295A1 (en) 2017-08-31

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